Liquid crystal display device

ABSTRACT

A liquid crystal display device includes: a pair of substrates, at least one of which is transparent; a liquid crystal layer placed between the pair of substrates; an electrode group, formed on at least one of the pair of substrates, for applying an electric field to the liquid crystal layer; and an alignment control film placed on at least one of the pair of substrates, in which the alignment control film is formed of polyimide and a precursor of the polyimide, each of the polyimide and the precursor of the polyimide contains, as a material, a specific cyclobutanetetracarboxylic acid dianhydride derivative and aromatic diamine, and the alignment control film is provided with alignment capability by photo-alignment treatment.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a continuation application of U.S. application Ser.No. 13/028,360, filed Feb. 16, 2011, the contents of which areincorporated herein by reference.

The present application claims priority from Japanese application JP2010-052318 filed on Mar. 9, 2010, the content of which is herebyincorporated by reference into this application.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a liquid crystal display device.

2. Description of the Related Art

Japanese Patent Application Laid-open No. 2009-48174, as a related art,aims to provide a liquid crystal alignment agent with a high-voltageretention ratio and a low image-sticking property, and discloses theprovision of a liquid crystal alignment agent which is composed ofpolyamide acid obtained by using, as at least a part of thetetracarboxylic acid dianhydride and the diamine compound,1,2,3,4-cyclobutanetetracarboxylic acid dianhydride derivative, and1,4-diaminocyclohexane, bicyclo[2.2.1]heptane-2,6-bis(methylamine),1,3-bis(aminomethyl)cyclohexane, isophorone, or an alkyl substitutionproduct of those diamines; an imidized polymer; or a mixture withanother imidized polymer, and which has a ratio of an amic acid bondunit of 5 to 80%. The liquid crystal alignment agent disclosed inJapanese Patent Application Laid-open No. 2009-48174 is provided withalignment capability by rubbing alignment treatment.

SUMMARY OF THE INVENTION

However, the rubbing alignment treatment includes a step of allowing anorganic coating film and a cloth to rub against each other physically.Therefore, unwanted shavings may be generated on the surface of thealignment film formed. The shavings cause display defects in a liquidcrystal display device. Consequently, there is a demand for theestablishment of clean alignment treatment, e.g., photo-alignmenttreatment that can replace the rubbing alignment treatment.

The photo-alignment treatment is a method of providing a surface of anorganic coating film with alignment capability through irradiation ofsubstantially linearly polarized light onto the surface of the organiccoating film formed on the surface of a substrate. In order toeffectively utilize the energy of light to be irradiated, it isnecessary to use a liquid crystal alignment agent with high sensitivitywith respect to light.

An object of the present invention is to provide a liquid crystaldisplay device having an alignment control film with high sensitivitywith respect to light. Further, the above-mentioned object and otherobjects, and novel features of the present invention are clarified bythe descriptions and the attached drawings of the specification.

A liquid crystal display device according to the present inventionincludes:

a pair of substrates, at least one of which is transparent;

a liquid crystal layer placed between the pair of substrates;

an electrode group, formed on at least one of the pair of substrates,for applying an electric field to the liquid crystal layer; and

an alignment control film placed on at least one of the pair ofsubstrates,

in which the alignment control film is formed of polyimide and aprecursor of the polyimide,

each of the polyimide and the precursor of the polyimide contains, as amaterial, a cyclobutanetetracarboxylic acid dianhydride derivativerepresented by the following chemical formula (1) and aromatic diamine,and

the alignment control film is provided with alignment capability byphoto-alignment treatment:

where at least one of Z¹ to Z⁴ is a substituent represented by —NR₂,—SR, —OH, —COR, —(CH₂)_(n)—COOR, —CN, or —NO₂ (R's each independentlyrepresent a hydrogen atom or an alkyl group having a carbon number of 1to 4, and n represents an integer of 0 to 2), and the others arehydrogen atoms.

Further, the aromatic diamine may contain at least one kind of aromaticdiamines selected from the compound group represented by the followingchemical formulae (101) to (110):

where X's each independently have any one of the following structures:—CH₂—, —CO—, —O—, —NH—, —CO—NH—, —S—, —SO—, and —SO₂—.

Further, the aromatic diamine may contain at least two different kindsof aromatic diamines selected from the compound group represented by thechemical formulae (101) to (110).

Further, a tetracarboxylic acid dianhydride used as a material for thepolyimide and the precursor of the polyimide may contain1,2,3,4-cyclobutanetetracarboxylic acid dianhydride derivativerepresented by the chemical formula (1) in a ratio of 70 mol % to 100mol %.

Further, in the liquid crystal display device according to the presentinvention, each of the polyimide and the precursor of the polyimide mayfurther contain, as a material, 1,2,3,4-cyclobutanetetracarboxylic aciddianhydride derivative represented by the following chemical formula(2):

where at least one of Y¹ to Y⁴ is a methyl group or a methoxy group, andthe others are hydrogen atoms.

In the liquid crystal display device according to the present invention,the precursor of the polyimide may contain a polyamide acid alkyl esterhaving an alkyl group of a carbon number of 1 to 4. Further, theelectrode group may be formed on only any one of the pair of substrates.In addition, a pretilt angle of the liquid crystal layer is 1 degree orless.

Further, at least two of Z¹ to Z⁴ in the chemical formula (1) may besubstituents each represented by —NR₂, —SR, —OH, —COR, —(CH₂)_(n)—COOR,—CN, or —NO₂ (R's each independently represent a hydrogen atom or analkyl group having a carbon number of 1 to 4, and n represents aninteger of 0 to 2), and the others may be hydrogen atoms.

Further, each of the polyimide and the precursor of the polyimide maycontain, as a material, at least two kinds of thecyclobutanetetracarboxylic acid dianhydride derivatives each representedby the chemical formula (1) and having different number of substituents.

According to the present invention, the liquid crystal display devicehaving an alignment control film with high sensitivity with respect tolight can be provided. The other effects of the present invention areclarified from the entire description of the specification.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic cross-sectional view in the vicinity of one pixelof a liquid crystal display device according to Example 1.

FIG. 2A is a schematic plan view of an active matrix substrateillustrating a configuration in the vicinity of one pixel of the liquidcrystal display device according to Example 1.

FIG. 2B is a cross-sectional view taken along the line 2B of FIG. 2A.

FIG. 2C is a cross-sectional view taken along the line 2 c of FIG. 2A.

FIG. 3 is a schematic cross-sectional view in the vicinity of one pixelof a liquid crystal display device according to Example 2.

FIG. 4A is a schematic plan view of an active matrix substrateillustrating a configuration in the vicinity of one pixel of the liquidcrystal display device according to Example 2.

FIG. 4B is a cross-sectional view taken along the line 4B of FIG. 4A.

FIG. 4C is a cross-sectional view taken along the line 4C of FIG. 4A.

FIG. 5 is a schematic cross-sectional view in the vicinity of one pixelof a liquid crystal display device according to Example 3.

FIG. 6 is a schematic cross-sectional view in the vicinity of one pixelof a liquid crystal display device according to Example 4.

FIG. 7 is a schematic cross-sectional view in the vicinity of one pixelof a liquid crystal display device according to Example 5.

FIG. 8 is a schematic plan view of an active matrix substrateillustrating a configuration in the vicinity of one pixel of the liquidcrystal display device according to Example 5.

DETAILED DESCRIPTION OF THE INVENTION

As a rubbing-less alignment method for solving the problems of therubbing alignment method, a photo-alignment method involving irradiationof light has been proposed and studied. However, the photo-alignmentmethod involves the following practical problems. In polymer materialsin each of which a light reactive group is introduced into a polymerside chain typified by polyvinyl cinnamate, and the like, thermalstability of alignment is not sufficient, and hence sufficientreliability is not obtained yet in terms of practicality.

Further, in this case, it is conceivable that the structural site thatdevelops the alignment of liquid crystal is a polymer side chainportion. Therefore, the above-mentioned alignment method is not alwayspreferred in more uniformly aligning liquid crystal molecules andobtaining stronger alignment.

Further, when a low-molecular dichroic dye is dispersed in a polymer,the dye per se that aligns the liquid crystal has a low molecularweight, and there remains a practical problem in view of the thermal oroptical reliability.

A photo-alignment method using photolysis of cyclobutane-based polyimideis an effective method high in the stability of alignment. However, inrecent years, there is an increasing need for the stability ofalignment, and the conventional cyclobutane-based polyimide materialcannot satisfy this need. Further, the cyclobutane-based polyimiderequires a large amount of light for light reaction, and hence has aproblem of a low production throughput.

An object of the present invention is to provide a liquid crystaldisplay device having an alignment control film with high sensitivitywith respect to light. Thus, a liquid crystal display device isprovided, which solves such a problem that a production margin ofalignment treatment is small, reduces occurrences of display defectscaused by fluctuation in an initial alignment direction, realizes stableliquid crystal alignment, and has high definition image quality with acontrast ratio enhanced.

In the liquid crystal display device according to the present invention,the alignment control film is formed of polyimide and a precursor of thepolyimide, each of the polyimide and the precursor of the polyimidecontains, as a material, a cyclobutanetetracarboxylic acid dianhydridederivative represented by the following chemical formula (1) andaromatic diamine, and the alignment control film is provided withalignment capability by photo-alignment treatment:

where at least one of Z¹ to Z⁴ is a substituent represented by —NR₂,—SR, —OH, —COR, —(CH₂)_(n)—COOR, —CN, or —NO₂ (R's each independentlyrepresent a hydrogen atom or an alkyl group having a carbon number of 1to 4, and n represents an integer of 0 to 2), and the others arehydrogen atoms.

Further, R's may each independently represent a hydrogen atom or analkyl group having a carbon number of 1 to 3, and n may represent aninteger of 0 to 2. Further, R's may each independently represent ahydrogen atom or an alkyl group having a carbon number of 1 or 2, and nmay represent an integer of 0 to 2. Further, R's may each independentlyrepresent a hydrogen atom or a methyl group, and n may represent aninteger of 0 to 2.

A cyclobutanetetracarboxylic acid dianhydride derivative represented bythe chemical formula (1) to be a material for polyimide and a precursorthereof forming an alignment control film according to the presentinvention is exemplified by, for example, the compound group Brepresented by the following the chemical formulae (B-1) to (B-18). Thecompounds represented by the compound group B each merely show anexample, and the derivative is not limited thereto.

where R¹'s in the compounds represented by the compound group B eachindependently represent a hydrogen atom or an alkyl group having acarbon number of 1 to 4, and n represents an integer of 0 to 2.

Of the above-mentioned compound group B, (B-1), (B-2), (B-3), (B-4),(B-5), (B-6), (B-7), and (B-8) each have a high light reactivity, inparticular, (B-1), (B-2), and (B-3) each have a very high lightreactivity, thereby being particularly effective.

More specifically, in the compound represented by the above-mentionedchemical formula (1), it is preferred that at least one of Z¹ to Z⁴ be asubstituent represented by —NR₂ (R's each independently represent ahydrogen atom or an alkyl group having a carbon number of 1 to 4), andthe others are hydrogen atoms. Further, R's may each independentlyrepresent a hydrogen atom or an alkyl group having a carbon number of 1to 3, and n may represent an integer of 0 to 2. Further, R's may eachindependently represent a hydrogen atom or an alkyl group having acarbon number of 1 to 2, and n may represent an integer of 0 to 2.Further, R's may each independently represent a hydrogen atom or amethyl group, and n may represent an integer of 0 to 2.

Further, in the compound represented by the above-mentioned chemicalformula (1), at least one of Z¹ to Z⁴ may be a substituent representedby —NHR (R's each independently represent a hydrogen atom or an alkylgroup having a carbon number of 1 to 4), and the others may be hydrogenatoms. Further, R's may each independently represent a hydrogen atom oran alkyl group having a carbon number of 1 to 3, and n may represent aninteger of 0 to 2. Further, R's may each independently represent ahydrogen atom or an alkyl group having a carbon number of 1 to 2, and nmay represent an integer of 0 to 2. Further, R's may each independentlyrepresent a hydrogen atom or a methyl group, and n may represent aninteger of 0 to 2.

Further, in the compound represented by the above-mentioned chemicalformula (1), at least one of Z¹ to Z⁴ may be a substituent representedby —NH₂, and the others may be hydrogen atoms.

Further, it is preferred that polyimide and a precursor thereof formingthe alignment control film in the display device according to thepresent invention further contain a cyclobutanetetracarboxylic aciddianhydride derivative represented by the following chemical formula (2)as a material in addition to the compound group B:

where at least one of Y¹ to Y⁴ is a methyl group or a methoxy group, andthe others are hydrogen atoms.

Further, at least two of Y¹ to Y⁴ in the chemical formula (2) may bemethyl groups or methoxy groups, and the others may be hydrogen atoms.Further, at least one of Y¹ to Y⁴ in the chemical formula (2) may be amethyl group, and the others may be hydrogen atoms or methoxy groups.Further, at least two of Y¹ to Y⁴ in the chemical formula (2) may bemethyl groups, and the others may be hydrogen atoms or methoxy groups.

A specific example of the cyclobutanetetracarboxylic acid dianhydridederivative represented by the chemical formula (2) is shown in thecompound group C represented by the following chemical formulae (C-1) to(C-6). The compounds shown in the compound group C each merely show anexample, and the derivative is not limited thereto.

It is particularly effective to contain the cyclobutanetetracarboxylicacid dianhydride derivative represented by the above-mentioned compoundgroup C because liquid crystal alignment stability is enhanced.

Further, it is preferred that each of polyimide and a precursor thereofforming the alignment control film in the display device according tothe present invention contain, as a material, at least one kind ofaromatic diamines selected from the compound group represented by thefollowing chemical formulae (101) to (110):

where X's each independently have any one of the following structures:—CH₂—, —CO—, —O—, —NH—, —CO—NH—, —S—, —SO—, and —SO₂—.

A group of compounds A represented by the chemical formulae (A-1) to(A-67) below are given as specific structural examples of the aromaticdiamine, which serves as a raw material for the polyimide and thepolyimide precursor each forming the alignment control film according tothe present invention. Each of those structures is merely an example ofspecific chemical structures, and the present invention is not limitedto those structures.

Among the above-mentioned group of compounds A, (A-1), (A-4), (A-8),(A-19), (A-21), (A-22), (A-28), (A-29), (A-30), (A-32), (A-47), and(A-53) is particularly preferred because of the satisfactory liquidcrystal alignment property.

Further, the precursor of the polyimide forming the alignment controlfilm according to the present invention is characterized by beingpolyamide acid and a polyamide acid alkyl ester. As described in thefollowing technical document 1, polyamide acid is obtained by stirringand polymerizing a diamine compound and a tetracarboxylic aciddianhydride in an organic solvent.

Technical document 1: Latest polyimide, edited by Polyimide Society ofJapan, issued by NTS (2002)

Specifically, a diamine compound is dissolved in a polar amide solventsuch as NMP. The tetracarboxylic dianhydride having substantially thesame moles as those of the diamine compound is added to the solution,and stirred at room temperature. Then, a ring-opening additionpolymerization reaction is advanced between the tetracarboxylicdianhydride and the diamine compound in accordance with the dissolutionof the tetracarboxylic dianhydride to obtain a polyamide acid having ahigh molecular weight. Further, in the case of the polyamide acid ester,a chlorinating reagent such as thionyl chloride is allowed to react witha diester dicarboxylic acid obtained by allowing an alcohol to reactwith a tetracarboxylic dianhydride, to thereby obtain a high-reactivediester dicarboxylic chloride. The diester dicarboxylic chloride isallowed to react with a diamine compound for polycondensation to obtaina polyamide acid alkyl ester.

In this situation, a plurality of kinds of diamine compounds andtetracarboxylic dianhydrides as raw materials may be mixed together, tothereby obtain a copolymer in which a plurality of chemical species arepolymerized in one polymer chain.

When a plurality of kinds of aromatic diamine components as shown in theabove-mentioned group of compounds A are mixed together, the absorptionwavelength range of the generated polyimide is widened. Therefore, thespectrum of a light source for emission can be effectively utilized.

More specifically, in the polyimide and the precursor thereof formingthe alignment control film according to the present invention, it ispreferred that the aromatic diamine contain at least two different kindsof aromatic diamines selected from the compound group represented by thechemical formulae (101) to (110).

Further, diamine used as a material for a polyimide precursor formingthe alignment control film according to the present invention containsat least one kind of aromatic diamines selected from the compound grouprepresented by the chemical formulae (101) to (110) preferably in anamount of 50 mol % to 100 mol %, more preferably in an amount of 70 mol% to 100 mol %, particularly preferably in an amount of 80 mol % to 100mol %. Such configuration enhances the light reactivity, and thealignment stability of liquid crystal is enhanced.

Further, each of the polyimide and the precursor thereof forming thealignment control film according to the present invention contains, as amaterial, at least one kind of the cyclobutanetetracarboxylic aciddianhydride derivatives represented by the chemical formula (1) and alsoexemplified by the compound group B preferably in an amount of 70 mol %to 100 mol %, more preferably in an amount of 80 mol % to 100 mol %,particularly preferably in an amount of 90 mol % to 100 mol %. Suchconfiguration enhances the light reactivity, and the alignment stabilityof liquid crystal is also enhanced.

Further, in the case where a plurality of substituents of Z¹ to Z⁴ inthe chemical formula (1) are substituents each represented by —NR₂, —SR,—OH, —COR, —(CB₂)_(n)—COOR, —CN, or —NO₂ (R's each independentlyrepresent a hydrogen atom or an alkyl group having a carbon number of 1to 4, and n represents an integer of 0 to 2), the light reactivity isenhanced further, and the alignment stability of liquid crystal is alsoenhanced.

More specifically, it is preferred that at least two of Z¹ to Z⁴ in thechemical formula (1) be substituents each represented by —NR₂, —SR, —OH,—COR, —(CH₂)_(n)—COOR, —CN, or —NO₂ (R's each independently represent ahydrogen atom or an alkyl group having a carbon number of 1 to 4, and nrepresents an integer of 0 to 2), and the others are hydrogen atoms.

Further, as the substituents each represented by —NR₂, —SR, —OH, —COR,—(CH₂)_(n)—COOR, —CN, or —NO₂ (R's each independently represent ahydrogen atom or an alkyl group having a carbon number of 1 to 4, and nrepresents an integer of 0 to 2) are more substituted in the chemicalformula (1), the light reactivity is enhanced more, and the alignmentstability of liquid crystal is also enhanced.

Incidentally, in the case where a cyclobutanetetracarboxylic aciddianhydride derivative represented by the chemical formula (1) and alsoexemplified by the compound group B is used as a simple substance, whenthe cyclobutanetetracarboxylic acid dianhydride derivative has such astructure that a ring-opening addition polymerization reactivity withdiamine is low, a ring-opening addition polymerization reaction does notproceed sufficiently, and hence a high molecular weight substance maynot be obtained.

The reason for this cannot be determined uniquely because it may varydepending upon the reaction conditions of the ring-opening additionpolymerization reaction. For example, it is considered that thering-opening addition polymerization reaction does not proceedsufficiently depending upon the combination of the number and kinds ofsubstituents contained in the structure of thecyclobutanetetracarboxylic acid dianhydride derivative.

If the ring-opening addition polymerization reaction does not proceedsufficiently, the molecular weight of the polyimide to be formed and theprecursor thereof decreases to degrade a film formation property, whichmay cause such a problem that the film surface becomes uneven. However,the above-mentioned problem can be solved by using a mixture of aplurality of kinds of cyclobutanetetracarboxylic acid dianhydridederivatives having different ring-opening addition polymerizationreactivities with aromatic diamine, to thereby obtain a polyimide and aprecursor thereof having a sufficiently high molecular weight.

For example, it is preferred that each of the polyimide and theprecursor thereof contain, as a material, at least two kinds ofcyclobutanetetracarboxylic acid dianhydride derivatives having differentnumber of substituents, represented by the chemical formula (1). Wheneach of the polyimide and the precursor thereof contains, as a material,at least two kinds of cyclobutanetetracarboxylic acid dianhydridederivatives having different number of substituents, represented by thechemical formula (1), an alignment control film having a high lightreactivity and alignment stability of liquid crystal can be formed.

For example, when each of the polyimide and the precursor thereofcontains, as a material, a cyclobutanetetracarboxylic acid dianhydridederivative (one of Z¹ to Z⁴ is a substituent represented by —NR₂, —SR,—OH, —COR, —(CH₂)_(n)—COOR, —CN, or —NO₂, R's each independentlyrepresent a hydrogen atom or an alkyl group having a carbon number of 1to 4, and n represents an integer of 0 to 2.) represented by thechemical formula (1) having one substituent, and thecyclobutanetetracarboxylic acid dianhydride derivative (one of Z¹ to Z⁴is a substituent represented by —NR₂, —SR, —OH, —COR, —(CH₂)_(n)—COOR,—CN, or —NO₂, R's each independently represent a hydrogen atom or analkyl group having a carbon number of 1 to 4, and n represents aninteger of 0 to 2.) represented by the chemical formula (1) having 2, 3,or 4 substituents, an alignment control film having a high lightreactivity and alignment stability of liquid crystal can be formed.

The polyimide forming the alignment control film according to thepresent invention is characterized by being obtained by allowing theimidization reaction of polyamide acid or a polyamide acid ester that isa precursor of the polyamide to proceed by heating or chemicalimidization. A plurality of kinds of polyimide precursors may be mixed,and for example, polyamide acid and a polyamide acid ester may be mixed.

Further, it is not necessarily required that the imidization reactionproceeds 100% in this case. The imidization reaction proceeds preferably50% to 100%, more preferably 60% to 95%, still more preferably 70% to90% of the total reaction. As the degree of progress of the imidizationreaction is higher, light alignment property and the alignment stabilityof liquid crystal are more enhanced. However, when the degree ofprogress is too high, the specific resistance of the alignment controlfilm becomes too high, which is not preferred in terms of electricalproperties.

The alignment control film according to the present invention can beused by blending a material having a low specific resistance. This iseffective because the specific resistance of the alignment control filmcan be decreased, and consequently, burning is hard to occur. Thematerial having a low resistance may be another polymer having a highelectric conductivity to be mixed with a polyimide and a precursorthereof. Aromatic diamine that has no side chain component having acarbon number of at least 2 may be used as a material for the polyimideand the precursor thereof.

It is also desired that the molecular weight of the polyimide formingthe alignment control film be higher, and a polyamide acid alkyl esteris more preferred because the reduction in molecular weight duringheating does not occur unlike polyamide acid, which enhances thealignment stability of liquid crystal.

When cyclobutane-based polyimide is irradiated with light, a photolyticreaction involving the cleavage of the ring structure of cyclobutane togenerate a maleimide terminal occurs. As the reaction speed of thephotolytic reaction is higher, the reaction proceeds with less lightamount, therefore, there is an advantage of an increase in throughput interms of production.

However, there is such a problem that the light reaction efficiency ofthe conventional cyclobutane-based polyimide is low, which isinsufficient for the production process. The inventors of the presentinvention found that, when a certain kind of substituent is introducedinto a cyclobutane ring, a photolytic reaction proceeds very fast. Thecyclobutane-based polyimide according to the present invention has veryhigh light reaction efficiency, and hence has features of a highthroughput and excellent alignment stability.

Hereinafter, examples of the present invention are described in detailwith reference to the accompanying drawings. The alignment control filmaccording to the present invention, which is used in the examples, ismerely an example, and the same effects have been confirmed in otherstructures. In the following description, a substrate on which an activeelement such as a thin film transistor is formed is called “activematrix substrate”. Further, when a counter substrate is provided with acolor filter, the substrate is also called “color filter substrate”.Further, in the present invention, a desired contrast as a target is500:1 or more, and a target period of time when the residual image iseliminated is desirably 5 minutes or less. The period of time when theresidual image is eliminated is determined according to a method definedin the following examples.

EXAMPLES Example 1

FIG. 1 is a schematic cross-sectional view in the vicinity of one pixelof a liquid crystal display device according to Example 1. Further, FIG.2A is a schematic plan view of an active matrix substrate illustrating aconfiguration in the vicinity of one pixel of the liquid crystal displaydevice according to Example 1. FIG. 2B is a cross-sectional view takenalong the line 2B of FIG. 2A. FIG. 2C is a cross-sectional view takenalong the line 2C of FIG. 2A. Further, FIG. 1 corresponds to apart ofthe cross-section taken along the line 2B of FIG. 2A.

FIGS. 2B and 2C emphasize and schematically illustrate configurations ofmain portions, and do not correspond one by one to cut portions of theline 2B and the line 2C in FIG. 2A. For example, a semiconductor film116 is not illustrated in FIG. 2B, and only one through-hole 118 thatconnects each common electrode 103 and a common line 120 isrepresentatively illustrated in FIG. 2C.

In this example, scanning lines (gate electrodes) 104 and the commonelectrode line (common line) 120 which are made of chrome (Cr) arearranged on a glass substrate 101 as the active matrix substrate, and agate insulating film 107 made of silicon nitride is so formed as tocover the gate electrodes 104 and the common line 120.

Further, the semiconductor film 116 made of amorphous silicon orpolysilicon is arranged above each of the gate electrodes 104 throughthe gate insulating film 107, and functions as an active layer of eachthin film transistor (TFT) 115 serving as the active element. Further,each signal line (drain electrode) 106 and each pixel electrode (sourceelectrode) 105 which are made of chrome/molybdenum (Cr.Mo) are soarranged as to be superimposed on a part of the pattern of thesemiconductor film 116, and a protective insulating film 108 made ofsilicon nitride is so formed as to cover all of those components.

Further, as illustrated in FIG. 2C, the common electrodes 103 thatconnect to the common line 120 through the through-hole 118 formedthrough the gate insulating film 107 and the protective insulating film108 are arranged on an overcoat layer (organic protective film) 112.Further, as illustrated in FIG. 2A, the common electrodes 103 drawn fromthe common line 120 through the through-hole 118 are so formed as toface the pixel electrodes 105 in a region of one pixel in a planarfashion.

In this example, the pixel electrodes 105 are arranged below theprotective insulating film 108 which is disposed below the organicprotective film 112, and the common electrodes 103 are arranged on theorganic protective film 112. One pixel is configured in a regionsandwiched between the plurality of pixel electrodes 105 and the commonelectrodes 103. Further, an alignment control film 109 is formed on thesurface of the active matrix substrate on which the unit pixelsconfigured as described above are arranged in matrix, that is, on theorganic protective film 112 on which the common electrodes 103 areformed.

On the other hand, as illustrated in FIG. 1, a color filter layer 111 isarranged on the glass substrate 102 forming the counter substrate so asto be partitioned by a light shield film (black matrix) 113 for eachpixel. Further, the color filter layer 111 and the light shield film 113are covered with the organic protective film 112 made of a transparentinsulating material. Further, the alignment control film 109 is alsoformed on the organic protective film 112 to configure a color filtersubstrate.

Those alignment control films 109 are imparted liquid crystal alignmentcapability by irradiation of linearly polarized ultraviolet rays whichare extracted with the use of a pile polarizer in which quartz platesare laminated on each other with a high-pressure mercury lamp as a lightsource.

The glass substrate 101 forming the active matrix substrate and theglass substrate 102 forming the color filter substrate are arranged toface each other at the surfaces of the alignment control films 109, anda liquid crystal layer (liquid crystal composition layer) 110 b made upof liquid crystal molecules 110 a is arranged between the glasssubstrate 101 and the glass substrate 102. Further, on the respectiveouter surfaces of the glass substrate 101 forming the active matrixsubstrate and the glass substrate 102 forming the color filtersubstrate, polarization plates 114 are formed.

In the above-mentioned manner, the active matrix liquid crystal displaydevice (TFT liquid crystal display device) using the thin filmtransistor (TFT) is configured. In the TFT liquid crystal displaydevice, the liquid crystal molecules 110 a forming the liquid crystalcomposition layer 110 b are aligned substantially in parallel to thesurfaces of the glass substrates 101 and 102 which face each other atthe time of applying no electric field. The liquid crystal molecules 110a are homogeneously aligned in a state in which the liquid crystalmolecules 110 a are directed in an initial alignment direction regulatedby the photo-alignment process.

Here, when a voltage is applied to the gate electrodes 104 to turn onthe TFT 115, an electric field 117 is applied to the liquid crystalcomposition layer 110 b due to a potential difference between the pixelelectrode 105 and the common electrodes 103. The liquid crystalmolecules 110 a forming the liquid crystal composition layer 110 b isturned to the electric field direction due to an interaction of adielectric anisotropy of the liquid crystal composition layer 110 b andthe electric field. In this situation, the refractive anisotropy of theliquid crystal composition layer 110 b and the action of thepolarization plates 114 can change the light transmittance of the liquidcrystal display device for display.

Further, the organic protective film 112 may be made of a thermosettingresin such as an acrylic resin, an epoxy acrylic resin, or a polyimideresin which is excellent in insulating property and transparency.Further, the organic protective film 112 may be made of a light curingtransparent resin, or an inorganic material such as a polysiloxaneresin. Further, the organic protective film 112 may also function as thealignment control film 109.

As described above, according to this example, the liquid crystalalignment control capability of the alignment control film 109 isperformed by using not the rubbing alignment process that directly rubsthe alignment control film 109 with a buff cloth, but the non-contactphoto-alignment method. As a result, uniform alignment can be given tothe entire surface of the display region without local disturbance ofalignment in the vicinity of the electrodes.

In general, in the IPS system, no interface tilt with the substratesurface is required in principle unlike the vertical electric fieldsystem represented by the conventional TN system. It is known that theviewing angle characteristic is more improved as the interface tiltangle becomes smaller. The smaller interface tilt angle is desired evenin the photo-alignment control film. In particular, when the interfacetilt angle is set to 1 degree or less, changes in color and brightnessdue to the viewing angle of the liquid crystal display device can beremarkably suppressed, which is effective.

Next, as a method of manufacturing the liquid crystal display deviceaccording to this example, the formation of the alignment control filmby using the rubbingless alignment method for the liquid crystalalignment control film is described. A flow of a process of forming thealignment control film according to this example includes the followingprocesses (1) to (4).

(1) Coating and formation of the alignment control film (a uniformcoating film is formed on the entire surface of the display region).

(2) Imidization baking of the alignment control film (removal of varnishsolvent and polyimidization high in heat resistance are enhanced).

(3) Impartation of the liquid crystal alignment capability byirradiation of the polarized light (the uniform alignment capability isimparted to the display region).

(4) Enhancement and stabilization of the alignment capability (byheating, infrared radiation, far infrared radiation, electron beamirradiation, and radiation exposure).

The alignment control film is formed through the above-mentioned fourprocesses. However, the present invention is not limited to the order ofthe above-mentioned processes (1) to (4). Moreover, further effects areexpected in the case of the following processes (a) and (b).

(a) The above-mentioned processes (3) and (4) are so processed as totemporally overlap with each other to accelerate the liquid crystalalignment capability impartation and induce the cross-linking reactionor the like. As a result, the alignment control film can be furthereffectively formed.

(b) In the case of using the heating, the infrared radiation, and thefar infrared radiation of the above-mentioned process (4), theabove-mentioned processes (2), (3), and (4) are allowed to temporallyoverlap with each other. As a result, the above-mentioned process (4)can also function as the imidization process of the above-mentionedprocess (2), and hence the alignment control film can be formed in ashort time.

Next, a specific manufacturing method of this example is described. Aglass substrate having a thickness of 0.7 mm whose surface has beenpolished is used as the glass substrate 101 forming the active matrixsubstrate and the glass substrate 102 forming the color filtersubstrate. The thin film transistor 115 formed on the glass substrate101 includes the pixel electrode (source electrode) 105, the signal line(drain electrode) 106, the scanning line (gate electrode) 104, and theamorphous silicon 116.

All of the scanning lines 104, the common electrode line 120, the signalline 106, and the pixel electrode 105 were formed by patterning a chromefilm, and an interval between the pixel electrode 105 and the commonelectrode 103 was set to 7 μm. The common electrodes 103 and the pixelelectrode 105 were formed by using the chrome film which is low inresistance and easy in patterning. Alternatively, a transparentelectrode may be formed by using an ITO film to achieve the higherbrightness characteristic.

The gate insulating film 107 and the protective insulating film 108 weremade of silicon nitride, and the respective thicknesses were set to 0.3μm. An acrylic resin was coated on those films, and a heat treatment at220° C. for 1 hour was conducted to form the transparent and insulatingorganic protective film 112.

Then, the through-hole 118 was formed up to the common electrode line120 through the photolithography and etching process as illustrated inFIG. 2C, and the common electrodes 103 that connect to the commonelectrode line 120 were formed by patterning.

As a result, as illustrated in FIG. 2A, the pixel electrode 105 wasarranged among the three common electrodes 103 within the unit pixel(one pixel) to form the active matrix substrate which has 1024×3×768pixels, which includes 1024×3 (corresponding to R, G, and B) signallines 106 and 768 scanning lines 104.

In this example, various polyamide acids 1 to 5 synthesized inaccordance with the raw material compositions shown in Table 1 belowwere used for the alignment control film 109. Then, those alignmentcontrol films were used to manufacture five liquid crystal displaydevices. The polyamide acid was used to prepare a varnish with a resinconcentration of 5 wt %, DMAC of 60 wt %, γ-butyrolactone of 20 wt %,and butyl cellosolve of 15 wt %. The varnish was printed on an activematrix substrate, and imidized through a heat treatment, to thereby forma dense alignment control film 109 made of a polyimide and a polyamideacid with an imidization ratio of about 80% and a thickness of about 110nm.

TABLE 1 Tetracarboxylic acid dianhydride Alignment Diamine compoundCompound control Compound group A group B film No. (Mol %) (Mol %) R¹ n1-1 A-1 (100) B-1 (100) —H — 1-2 A-12 (100) B-5 (100) —CH₃ — 1-3 A-19(100) B-8 (100) —CH₃ — 1-4 A-21 (100) B-17 (100) — — 1-5 A-41 (100) B-18(100) — —

Likewise, the same polyamide acid amide varnish was also printed on thesurface of the other glass substrate 102 on which the ITO had beenformed, to thereby form the dense alignment control film 109 made of apolyimide and a polyamide acid with the imidization ratio of about 80%and the thickness of about 110 nm. In order to impart the liquid crystalalignment capability to the surface of the alignment control film 109,polarized ultraviolet (UV) rays were applied onto the alignment controlfilm 109. With the use of a high-pressure mercury lamp as the lightsource, the UV rays in a range of 240 nm to 320 nm were extractedthrough an interference filter. The extracted UV rays were linearlypolarized at the polarization ratio of about 10:1 by using a pilepolarizer in which quartz substrates were laminated on each other, andapplied with the irradiation energy of 1.5 J/cm². As a result, it wasfound that the alignment direction of the liquid crystal molecules onthe alignment control film surface was orthogonal to the polarizationdirection of the irradiated polarized UV rays.

Then, those two glass substrates 101 and 102 were faced each other atthe surfaces having the respective alignment control films 109 with theliquid crystal alignment capability. Spacers formed of dispersedspherical polymer beads were interposed between those two glasssubstrates 101 and 102, and a sealing material was coated on theperipheral portions of the glass substrates 101 and 102, to therebyassemble a liquid crystal display panel (hereinafter, also referred toas “cell”) forming the liquid crystal display device. The liquid crystalalignment directions of the two glass substrates 101 and 102 weresubstantially parallel to each other. A nematic liquid crystalcomposition A which was positive in the dielectric anisotropy Δ∈, 10.2(1 kHz, 20° C.) in the value of the dielectric anisotropy, 0.075(wavelength 590 nm, 20° C.) in the refractive anisotropy Δn, 7.0 pN intwisted elastic constant K2, and about 76° C. in nematic-to-isotropictransition temperature T (N−1) was injected into the cell in a vacuum,and sealed with a sealing material made of an ultraviolet curable resin.A liquid crystal panel in which the thickness (gap) of the liquidcrystal layer was 4.2 μm was manufactured.

The retardation (Δn·d) of this liquid crystal display panel is about0.31 μm. It is desired that Δn·d satisfy a range of 0.2 μm≦Δn·d≦0.5 μm,and when Δn·d exceeds this range, there arises such a problem that whitedisplay is colored. Further, a liquid crystal display panel of ahomogeneous alignment was manufactured by using the same alignmentcontrol film and the liquid crystal composition as those used in thispanel, and the pretilt angle of liquid crystal was measured through acrystal rotation method. The measurement result was about 0.2 degrees.This liquid crystal display panel was sandwiched between the twopolarization plates 114 so that the polarization transmission axis ofone polarization plate was so arranged to be substantially parallel tothe above-mentioned liquid crystal alignment direction, and thepolarization transmission axis of the other polarization plate was soarranged to be orthogonal to the former polarization transmission axis.After that, a drive circuit, a backlight, and the like were connectedfor modulation to obtain the active matrix liquid crystal displaydevice. In this example, a normally close characteristic in which darkdisplay was established with a low voltage, and bright display wasestablished with a high voltage was provided.

As a result of evaluating the display quality of the five liquid crystaldisplay devices according to this example, a wide viewing angle at thetime of the halftone display was confirmed as well as the high-gradedisplay of 500:1 in the contrast ratio. The contrast ratios of theliquid crystal display devices using diamine compounds (A-1), (A-19),and (A-21) exceed 600:1, which exhibit particularly satisfactory displayquality.

Further, in order to quantitatively measure the image-sticking and theresidual image of the five liquid crystal display devices according tothis example, an oscilloscope having the combination of photodiodes wasused for evaluation. First, a window pattern was displayed on a screenwith the maximum brightness for 10 hours. After that, the entire screenwas switched to the halftone display where the residual image was mostvisible, that is, in this example, the brightness of 10% of the maximumbrightness. The display quality was evaluated with a time until thepattern of an edge portion of the window pattern was eliminated as aresidual image relaxation time. However, the residual image relaxationtime permitted in this example is 5 minutes or less. As a result, theresidual image relaxation time was 5 minutes or less in the usetemperature range (0° C. to 50° C.). Even in the visual image qualityresidual image test, the sticking of the image and the displayunevenness caused by the residual image were not found at all.Therefore, the high display characteristic was obtained.

Comparative Example 1

Similar liquid crystal display devices were produced using atetracarboxylic acid dianhydride that is a material as a tetracarboxylicacid dianhydride derivative in the alignment control films 1 to 5. As aresult, an irradiation energy of 6 J/cm² or more was required forexhibiting the display properties equal to those in Example 1.

Example 2

FIG. 3 is a schematic cross-sectional view illustrating a vicinity ofone pixel in the liquid crystal display device according to Example 2.FIG. 4A is a schematic plan view of an active matrix substrateillustrating the configuration of the vicinity of one pixel of theliquid crystal display device according to Example 2. FIG. 4B is across-sectional view taken along the line 4B illustrated in FIG. 4A.FIG. 4C is a cross-sectional view taken along the line 4C illustrated inFIG. 4A.

Further, FIG. 4 is a schematic view of an active matrix substrateillustrating a configuration in the vicinity of one pixel of the liquidcrystal display device according to this example. FIG. 4A is a planview, FIG. 4B is a cross-sectional view taken along the line 4B of FIG.4A, and FIG. 4C is a cross-sectional view taken along the line 4C ofFIG. 4A. Further, FIG. 3 corresponds to apart of the cross-section takenalong the line 4B of FIG. 4A.

FIGS. 4B and 4C emphasize and schematically illustrate configurations ofmain portions, and do not correspond one by one to cut portions of theline 4B and the line 4C of FIG. 4A. For example, the semiconductor film116 is not illustrated in FIG. 4B.

In this example, the gate electrodes 104 and the common electrode line120 which are made of Cr are arranged on the glass substrate 101 formingthe active matrix substrate, and the gate insulating film 107 made ofsilicon nitride is so formed as to cover the gate electrodes 104 and thecommon electrode line 120. Further, the semiconductor film 116 made ofamorphous silicon or polysilicon is arranged above each of the gateelectrodes 104 through the gate insulating film 107, and functions as anactive layer of each thin film transistor 115 serving as the activeelement.

Further, each drain electrode 106 and each source electrode (pixelelectrode) 105 made of chrome/molybdenum are so arranged as to besuperimposed on a part of the pattern of the semiconductor film 116, andthe protective insulating film 108 made of silicon nitride is so formedas to coverall of those components. The organic protective film 112 isarranged on the protective insulating film 108. The organic protectivefilm 112 is made of, for example, a transparent material such as anacrylic resin. Further, the pixel electrode 105 is formed of atransparent electrode made of ITO (In₂O₃:Sn) or the like. The commonelectrode 103 is connected to the common electrode line 120 through thethrough-hole 118 that passes through the gate insulating film 107, theprotective insulating film 108, and the organic protective film 112.

In the case of applying an electric field for driving the liquidcrystal, the common electrode 103 paired with the pixel electrode 105 isso formed as to surround the region of one pixel in a planar fashion.Further, the common electrode 103 is arranged on the organic protectivefilm 112. The common electrode 103 is so arranged as to cover the drainelectrode 106, the scanning lines 104, and the thin film transistor 115which is an active element, which are disposed below when being viewedfrom the top. The common electrode 103 also functions as a light shieldlayer that shields light from the semiconductor film 116.

The alignment control film 109 is formed on the surface of the glasssubstrate 101 forming the active matrix substrate in which the unitpixels (one pixel) configured as described above are arranged in matrix,that is, on the organic protective film 112 and the common electrode 103formed on the organic protective film 112. On the other hand, on theglass substrate 102 forming the counter substrate, the alignment controlfilm 109 is formed on the organic protective film 112 formed on thecolor filter layer 111.

Here, like Example 1, the liquid crystal alignment capability isimparted to the alignment control film 109 by irradiation of linearlypolarized ultraviolet rays which are extracted with the use of a pilepolarizer in which quartz plates are laminated on each other with ahigh-pressure mercury lamp as a light source.

The glass substrate 101 and the counter glass substrate 102 are arrangedto face each other at the surfaces where the alignment control films 109are formed, and the liquid crystal composition layer 110 b made ofliquid crystal molecules 110 a are arranged between the glass substrate101 and the counter glass substrate 102. Further, on the respectiveouter surfaces of the glass substrate 101 and the counter glasssubstrate 102, the polarization plates 114 are formed.

As described above, also in this example, like Example 1 above, thepixel electrode 105 is arranged below the organic protective film 112and the protective insulating film 108, and the common electrode 103 isarranged above the pixel electrode 105 and the organic protective film112. Further, when the electric resistance of the common electrode 103is sufficiently low, the common electrode 103 can also function as thecommon electrode line 120 formed in the lowest layer. In this case, theformation of the common electrode line 120 disposed in the lowest layerand the processing of the through-hole 118 accompanied by the formationof the common electrode line 120 can be omitted.

In this example, as illustrated in FIG. 4A, one pixel is configured by aregion surrounded by the common electrodes 103 formed in a lattice, andone pixel is divided into four regions together with the pixel electrode105. Further, the pixel electrode 105 and the common electrodes 103 thatface the pixel electrode 105 are of a zigzag bent structure where thosecomponents are arranged in parallel to each other. One pixel forms aplurality of sub-pixels of two or more. With this structure, a change incolor tone within the plane is offset.

Next, a manufacturing method for the liquid crystal display deviceaccording to this example is described. A glass substrate having athickness of 0.7 mm whose surface has been polished is used as the glasssubstrate 101 and the glass substrate 102. The thin film transistor 115includes the pixel electrode (source electrode) 105, the signal line(drain electrode) 106, the scanning line (gate electrode) 104, and theamorphous silicon 116. The scanning line 104 was formed by patterning analuminum film, the common electrode line 120 and the signal line 106were formed by patterning a chrome film, and the pixel electrode 105 wasformed by patterning an ITO film. As illustrated in FIG. 4A, thecomponents other than the scanning line 104 were formed into electrodeline patterns which were bent in zigzag. In this situation, an angle ofbending was set to 10 degrees. The gate insulating film 107 and theprotective insulating film 108 were made of silicon nitride, and therespective thicknesses were set to 0.3 μm. Then, as illustrated in FIG.4C, the through-hole 118 having a diameter of about 10 μm was formedinto a cylindrical shape through the photolithography method and theetching process so as to extend up to the common electrode line 120. Anacrylic resin was coated on the through-hole 118, and a heat treatmentwas performed at 220° C. for 1 hour to form the transparent andinsulating organic protective film 112 which was about 4 in dielectricconstant at a thickness of about 1 μm. The roughness caused by a step ofthe pixel electrode 105 in the display region was flattened by theorganic protective film 112. Further, the roughness caused by a step ata boundary portion of the color filter layer 111 between the adjacentpixels was flattened by the organic protective film 112.

After that, the through-hole 118 was again etched to have a diameter ofabout 7 μm, and the common electrode 103 connected to the commonelectrode line 120 was formed on the through-hole 118 by patterning anITO film. In this situation, the interval between the pixel electrode105 and the common electrode 103 was set to 7 μm. Further, the commonelectrode 103 was formed in a lattice so as to cover the upper portionsof the signal line 106, the scanning lines 104, and the thin filmtransistor 115, and to surround the pixel, and also was formed so as tofunction as the light shield layer.

As a result, within the unit pixel, as illustrated in FIG. 4A, the pixelelectrode 105 was arranged among the three common electrodes 103 toobtain the active matrix substrate which had 1024×3×768 pixels,including 1024×3 (corresponding to R, G, and B) signal lines 106 and 768scanning lines 104.

In this example, various polyamide acid t-butyl esters 1 to 3synthesized in accordance with the raw material compositions shown inTable 2 below were used for the alignment control film 109. Then, thosealignment control films were used to manufacture three liquid crystaldisplay devices. The polyamide acid t-butyl ester was used to prepare avarnish with a resin concentration of 5 wt %, DMAC of 60 wt %,γ-butyrolactone of 20 wt %, and butyl cellosolve of 15 wt %. The varnishwas printed on an active matrix substrate, and imidized through a heattreatment to form a dense alignment control film 109 made of a polyimideand a polyamide acid t-butyl ester with an imidization ratio of about90% and a thickness of about 120 nm.

TABLE 2 Tetracarboxylic acid dianhydride Alignment Diamine compoundCompound control Compound group A group B film No. (Mol %) (Mol %) R¹ n2-1 A-1 (80) B-3 (70) —CH₃ — A-27 (20) B-16 (30) — — 2-2 A-12 (90) B-4(60) —CH₂CH₂CH₃ — A-42 (10) B-18 (40) — — 2-3 A-19 (60) B-9 (50) — —A-20 (40) B-6 (50) —CH₂CH₃ —

In the aligning method, the same polarized UV as that in Example 1 wasapplied with the irradiation energy of 1.5 J/cm². Then, those two glasssubstrates 101 and 102 are faced each other at the surfaces having thealignment control films. Spacers formed of dispersed spherical polymerbeads were interposed between those glass substrates, and a sealingmaterial was coated on the peripheral portions of the glass substratesto assemble a liquid crystal display panel. The liquid crystal alignmentdirections of those two glass substrates 101 and 102 were substantiallyparallel to each other.

A nematic liquid crystal composition A which was positive in thedielectric anisotropy Δ∈, 10.2 (1 kHz, 20° C.) in the value of thedielectric anisotropy, 0.075 (wavelength 590 nm, 20° C.) in therefractive anisotropy Δn, 7.0 pN in twisted elastic constant K2, andabout 76° C. in nematic-to-isotropic transition temperature T (N−1) wasinjected into the liquid crystal display panel in a vacuum, and sealedwith a sealing material made of an ultraviolet curable resin. A liquidcrystal panel in which a thickness (gap) of the liquid crystal layer was4.2 μm was manufactured. The retardation (Δnd) of this panel is about0.31 μm.

Further, a liquid crystal display panel of a homogeneous alignment wasmanufactured by using the same alignment control film and liquid crystalcomposition as those used in the liquid crystal display panel, and thepretilt angle of liquid crystal was measured through a crystal rotationmethod. The measurement result was about 0.2 degrees. This liquidcrystal display panel was sandwiched between the two polarization plates114 so that the polarization transmission axis of one polarization platewas so arranged to be substantially parallel to the above-mentionedliquid crystal alignment direction, and the polarization transmissionaxis of the other polarization plate was so arranged to be orthogonal tothe former polarization transmission axis. After that, a drive circuit,a backlight, and the like were connected for modulation to obtain theactive matrix liquid crystal display device. In this example, a normallyclose characteristic in which dark display is established with a lowvoltage, and bright display is established with a high voltage wasprovided.

Next, as a result of evaluating the display quality of the three liquidcrystal display devices according to this example, the aperture ratiowas higher than that in the liquid crystal display device of Example 1,and a wide viewing angle at the time of the halftone display wasconfirmed as well as the high-grade display of 500:1 in the contrastratio. The contrast ratios of the liquid crystal display devicescontaining 60 mol % or more of the diamine compounds (A-1) and (A-19)exceed 600:1, which exhibit particularly satisfactory display quality.Further, as a result of quantitatively evaluating the image-sticking andthe residual image relaxation time of the liquid crystal display devicesas in Example 1, the residual image relaxation time was 5 minutes orless in the use temperature range of 0° C. to 50° C., and even in thevisual image quality residual image test, the sticking of the image, andthe display unevenness caused by the residual image were not found atall, and the high display characteristic equivalent to Example 1 wasobtained.

Example 3

FIG. 5 is a schematic cross-sectional view of the vicinity of one pixelin a liquid crystal display device according to Example 3. In thefigure, the same symbols as those in the figures of the respectiveexamples correspond to identical function portions. As illustrated inFIG. 5, in this example, the pixel electrode 105 disposed below theprotective insulating film 108 is pulled up onto the organic protectivefilm 112 through the through-hole 118 so as to be arranged in the samelayer as that of the common electrode 103. In this configuration, avoltage for driving the liquid crystal can be further reduced.

In the TFT liquid crystal display device configured as described above,at the time of applying no electric field, the liquid crystal molecules110 a forming the liquid crystal composition layer 110 b are alignedsubstantially in parallel to the surfaces of the glass substrates 101and 102 which face each other. The liquid crystal molecules 110 a arehomogeneously aligned in a state in which the liquid crystal molecules110 a are directed in an initial alignment direction regulated by thephoto-alignment process. In this example, when a voltage is applied tothe gate electrodes 104 to turn on the thin film transistor 115, anelectric field 117 is applied to the liquid crystal composition layer110 b due to a potential difference between the pixel electrode 105 andthe common electrode 103. The liquid crystal molecules 110 a turn to theelectric field direction due to an interaction of a dielectricanisotropy of the liquid crystal composition and the electric field. Inthis situation, the dielectric anisotropy of the liquid crystalcomposition layer 110 b and the action of the polarization plates 114can change the light transmittance of the liquid crystal display devicefor display.

Hereinafter, a method of manufacturing the liquid crystal display deviceaccording to this example is described. As the glass substrates 101 and102, glass substrates each having a thickness of 0.7 mm whose surfaceshave been polished are used. The thin film transistor 115 includes thepixel electrode (source electrode) 105, the signal line (drainelectrode) 106, the scanning line (gate electrode) 104, and theamorphous silicon 116. The scanning lines 104 were formed by patterningan aluminum film. The common electrode line 120, the signal line 106,and the pixel electrode 105 were formed by patterning a chrome film. Thegate insulating film 107 and the protective insulating film 108 weremade of silicon nitride, and the respective thicknesses were set to 0.3μm. An acrylic resin was coated on those films, and a heat treatment wasperformed at 220° C. for 1 hour to form the transparent and insulatingorganic protective film 112 which was about 4 in the dielectric constantat a thickness of about 1.0 μm. The roughness caused by a step of thepixel electrode 105 in the display region was flattened by the organicprotective film 112. Further, the roughness caused by a step between theadjacent pixels was flattened by the organic protective film 112.

Then, as illustrated in FIG. 5, the through-hole 118 having a diameterof about 10 μm was formed into a cylindrical shape through thephotolithography method and the etching process so as to extend up tothe source electrode 105. The pixel electrode 105, which was connectedto the source electrode 105, was formed by patterning an ITO film on theupper portion of the through-hole 118. Further, in the common electrodeline 120, a through-hole was formed into a cylindrical shape with adiameter of about 10 μm, and an ITO film was patterned on the upperportion of the through-hole to form the common electrode 103. In thissituation, the interval between the pixel electrode 105 and the commonelectrode 103 was set to 7 μm, and the components other than thescanning lines 104 were formed into electrode line patterns which werebent in zigzag. In this situation, an angle of bending was set to 10degrees. Further, the common electrodes 103 were formed in a lattice soas to cover the upper portions of the signal line 106, the scanninglines 104, and the thin film transistor 115, and to surround the pixels.Thus, the common electrode 103 also functions as the light shield layer.

As a result, except that two kinds of through-holes were formed withinthe unit pixel, the pixel electrode 105 was arranged among the threecommon electrodes 103 substantially in the same manner as that ofExample 2. With this configuration, the active matrix substrate whichhad 1024×3×768 pixels, including of 1024×3 (corresponding to R, G, andB) signal lines 106 and 768 scanning lines 104 was formed.

As described above, the liquid crystal display device was manufacturedin the same manner as that of Example 2 as illustrated in FIG. 5, exceptfor the pixel configuration and the alignment control film to be used.

In this example, various polyamide acid ethyl esters 1 to 3 synthesizedin accordance with the raw material compositions shown in Table 3 belowwere used for the alignment control film 109. Then, those alignmentcontrol films were used to manufacture three liquid crystal displaydevices. The polyamide acid ethyl ester was used to prepare a varnishwith a resin concentration of 5 wt %, DMAC of 60 wt %, γ-butyrolactoneof 20 wt %, and butyl cellosolve of 15 wt %. The varnish was printed onan active matrix substrate, and imidized through a heat treatment toform a dense alignment control film 109 made of a polyimide and apolyamide acid ethyl ester with an imidization ratio of about 80% and athickness of about 140 nm.

TABLE 3 Tetracarboxylic acid dianhydride Alignment Diamine compoundCompound control Compound group A group B film No. (Mol %) (Mol %) R¹ n3-1 A-47 (70) B-3 (100) —CH₃ — A-60 (20) A-49 (10) 3-2 A-58 (60) B-1(80) —C(CH₃)₃ — A-44 (20) B-5 (20) H — A-33 (20) 3-3 A-26 (40) B-7 (50)—CH₃ — A-37 (40) B-10 (10) — — A-23 (20) B-12 (40) —CH₂CH₃ —

In the aligning method, the same polarized UV as that in Example 1 wasapplied with the irradiation energy of 1.5 J/cm².

Then, as a result of evaluating the display quality of the three liquidcrystal display devices according to this example, a wide viewing angleat the time of the halftone display was confirmed as well as thehigh-grade display equivalent to that of the liquid crystal displaydevices of Example 1. Further, as a result of quantitatively evaluatingthe image-sticking and the residual image relaxation time of the liquidcrystal display devices according to this example as in Example 1, theresidual image relaxation time was about 5 minutes or less, and even inthe visual image quality residual image test, the sticking of the imageand the display unevenness caused by the residual image were not foundat all, and the high display characteristic was obtained.

As illustrated in FIG. 5, in the case where the pixel electrode 105connected directly to the TFT 115 is formed on the uppermost surface ofthe substrate, and the thin alignment control film 109 is formed on thepixel electrode 105, when a normal rubbing alignment processing isperformed, electrostatic charge is generated due to rubbing, with theresult that the TFT 115 may be damaged through the pixel electrode inthe vicinity of the surface. In this case, the rubbinglessphoto-alignment process as in this example is very effective.

Example 4

FIG. 6 is a schematic cross-sectional view of the vicinity of one pixelin a liquid crystal display device according to Example 4. In thefigure, the same symbols as those in the figures of the respectiveexamples correspond to identical function portions.

This example employs a configuration in which a step due to electrodesand the like is large. In FIG. 6, the gate electrode 104 of each of thinfilm. transistor 115 and the common electrode 103 are formed in the samelayer, and the liquid crystal molecules 110 a turn to the electric fielddirection due to the electric field 117 caused by the common electrode103 and the pixel electrode 105.

Further, in the above-mentioned respective examples, a plurality ofdisplay regions, each of which is made up of the common electrode 103and the pixel electrode 105, can be provided in one pixel. When theplurality of display regions are provided in this manner, even if onepixel is larger, a distance between the pixel electrode 105 and thecommon electrode 103 can be shortened. Therefore, a voltage to beapplied for driving the liquid crystal can be decreased.

Further, in the above-mentioned respective examples, a material of thetransparent conductive film forming at least one of the pixel electrodeand the common electrode is not particularly restricted. However, takingthe ease of processing and high reliability into consideration, it isdesired to use a transparent conductive film of indium tin oxide (ITO)or any other ion-doped titanium oxide or ion-doped zinc oxide.

In the method of manufacturing the liquid crystal display deviceaccording to this example, glass substrates each having a thickness of0.7 mm whose surfaces have been polished are used as the glasssubstrates 101 and 102. The thin film transistor 115 includes the pixelelectrode (source electrode) 105, the signal line (drain electrode) 106,the scanning line (gate electrode) 104, and the amorphous silicon 116.All of the scanning line 104, the common electrode line 120, the signalline 106, the pixel electrode 105, and the common electrode 103 wereformed by patterning a chrome film, and an interval between the pixelelectrode 105 and the common electrodes 103 was set to 7 μm. The gateinsulating film 107 and the protective insulating film 108 were made ofsilicon nitride, and the respective thicknesses were set to 0.3 μm.

In this example, various polyamide acids 1 to 5 synthesized inaccordance with the raw material compositions shown in Table 4 belowwere used for the alignment control film 109. Then, those alignmentcontrol films were used to manufacture five liquid crystal displaydevices. The polyamide acid was used to prepare a varnish with a resinconcentration of 5 wt %, DMAC of 60 wt %, γ-butyrolactone of 20 wt %,and butyl cellosolve of 15 wt %. The varnish was printed on an activematrix substrate, and imidized through a heat treatment to form a densealignment control film 109 made of a polyimide and a polyamide acid withan imidization ratio of about 80% and a thickness of about 110 nm.

TABLE 4 Tetracarboxylic acid dianhydride Alignment Diamine compoundCompound control Compound group A group B film No. (Mol %) (Mol %) R¹ n4-1 A-64 (100) B-11 (50) —CH₃ — B-17 (50) — — 4-2 A-53 (100) B-14 (70)—H 1 B-14 (30) —CH₃ 2 4-3 A-22 (100) B-16 (10) —CH₃ — B-18 (10) — — B-8(80) H —

In the aligning method, the same polarized UV as that in Example 1 wasapplied with the irradiation energy of 1.5 J/cm². As a result, theactive matrix substrate which had 1024×3×768 pixels, including 1024×3(corresponding to R, G, and B) signal lines 106 and 768 scanning lines104, was formed.

As described above, the liquid crystal display device according to thisexample illustrated in FIG. 6 was manufactured in the same manner asthat of Example 1 except for the pixel structure.

Next, as a result of evaluating the display quality of three liquidcrystal display devices according to this example, a wide viewing angleat the time of the halftone display was confirmed as well as thehigh-grade display equivalent to that of the liquid crystal displaydevice of Example 1. The contrast ratio of the liquid crystal displaydevices using the diamine compounds (A-22) and (A-53) exceeded 600:1,which exhibited a particularly satisfactory display quality. Further, asa result of quantitatively evaluating the image-sticking and theresidual image relaxation time of the liquid crystal display devicesaccording to this example as in Example 1, the residual image relaxationtime was 5 minutes or less, and even in the visual image qualityresidual image test, the sticking of the image, and the displayunevenness caused by the residual image were not found at all, and thehigh display characteristic was obtained.

Example 5

FIG. 7 is a schematic cross-sectional view of the vicinity of one pixelin a liquid crystal display device according to Example 5. In thefigure, the same symbols as those in the figures of the respectiveexamples correspond to identical function portions. In this example, thepixel electrode 105 and the common electrode 103 are made of ITO, andthe common electrode 103 is formed of a solid electrode that covers thesubstantially entire pixel. With this configuration, the electrode canbe also used as a transmission portion so that the aperture ratio can beimproved. Further, the electrode interval can be shortened, and hencethe electric field can be efficiently applied to the liquid crystal.

FIG. 8 is a schematic plan view of an active matrix substrateillustrating the configuration of the vicinity of one pixel in theliquid crystal display device according to Example 5. FIG. 8 illustratesthe structures of the thin film transistor 115, the common electrode103, the pixel electrode 105, and the signal line 106.

In the method of manufacturing the liquid crystal display deviceaccording to this example, a glass substrate having a thickness of 0.7mm whose surface has been polished is used as the glass substrate 101.On the glass substrate 101, the gate insulating film 107 for preventingthe common electrode 103, the pixel electrode 105, the signal line 106,and the scanning lines 104 from being short-circuited, and theprotective insulating film 108 for protecting the thin film transistor115, the pixel electrode 105, and the signal line 106 are formed, tothereby provide a TFT substrate.

The thin film transistor 115 includes the pixel electrode (sourceelectrode) 105, the signal line (drain electrode) 106, the scanning line(gate electrode) 104, and the amorphous silicon 116. The scanning line(gate electrode) 104 is formed by patterning an aluminum film, thesignal line (drain electrode) 106 is formed by patterning a chrome film,and the common electrode 103 and the pixel electrode 105 are formed bypatterning ITO.

The gate insulating film 107 and the protective insulating film 108 weremade of silicon nitride, and the respective thicknesses were set to 0.2μm and 0.3 μm. A capacitative element was formed as a structure in whichthe gate insulating film 107 and the protective insulating film 108 weresandwiched between the pixel electrode 105 and the common electrode 103.

The pixel electrode 105 is so arranged as to overlap with an upper layerof the common electrode 103 having a solid shape. The number of pixelsis 1024×3×768, including 1024×3 (corresponding to R, G, and B) signallines 106 and 768 scanning lines 104.

On the glass substrate 102, the color filter layer 111 with the blackmatrix 113 is formed, to thereby provide a counter color filtersubstrate as in Example 1.

In this example, various polyamide acid methyl esters 1 to 5 synthesizedin accordance with the raw material compositions shown in Table 5 belowwere used for the alignment control film 109. Then, those alignmentcontrol films were used to manufacture five liquid crystal displaydevices. The polyamide acid methyl ester was used to prepare a varnishwith a resin concentration of 5 wt %, DMAC of 60 wt %, γ-butyrolactoneof 20 wt %, and butyl cellosolve of 15 wt %. The varnish was printed onan active matrix substrate, and imidized through a heat treatment toform a dense alignment control film 109 made of a polyimide and apolyamide acid methyl ester with an imidization ratio of about 70% and athickness of about 130 nm.

TABLE 5 Tetracarboxylic acid dianhydride Alignment Diamine compoundCompound control Compound group A group B film No. (Mol %) (Mol %) R¹ n5-1 A-1 (100) B-2 (100) —CH₃ — 5-2 A-1 (100) B-2 (80) —CH₃ — PMDA (20)5-3 A-1 (100) B-2 (70) —CH₃ — PMDA (30) 5-4 A-1 (90) B-6 (100) —CH₂CH₃ —A-29 (10) 5-5 A-19 (100) B-13 (20) —H 1 B-15 (80) — — PMDA: Pyromelliticacid dianhydride

Likewise, the same polyamide acid ethyl ester varnish was also printedon the surface of the other glass substrate 102 on which an ITO film hadbeen formed, and imidized through a heat treatment to form a densealignment control film 109 made of a polyimide and a polyamide acidmethyl ester with an imidization ratio of about 80% and a thickness ofabout 110 nm.

In the aligning method, the polarized UV was applied with theirradiation energy of 1.5 J/cm².

The alignment directions of the alignment control films 109 on the TFTsubstrate and the color filter substrate were substantially parallel toeach other. Polymer beads having an average grain diameter of 4 μm weredispersed as spacers between the substrates, and the liquid crystalmolecules 110 a were sandwiched between the TFT substrate and the colorfilter substrate. The liquid crystal molecules 110 a were made of thesame liquid crystal composition A as that in Example 1.

The two polarization plates 114 that sandwich the TFT substrate and thecolor filter substrate were arranged in crossed nicols. A normally closecharacteristic in which dark display is established with a low voltageand bright display is established with a high voltage was adopted.

Next, as a result of evaluating the display quality of the liquidcrystal display device according to this example, the aperture ratio washigher than that in the liquid crystal display device of Example 1, anda wide viewing angle at the time of the halftone display was confirmedas well as the high-grade display of 700:1 in the contrast ratio.Further, as a result of quantitatively evaluating the image-sticking andthe residual image relaxation time of the liquid crystal display devicesas in Example 1, the residual image relaxation time was 5 minutes orless in the use temperature range of 0° C. to 50° C., and even in thevisual image quality residual image test, the sticking of the image, andthe display unevenness caused by the residual image were not found atall, and the high display characteristic equivalent to Example 1 wasobtained.

Example 6

In this example, the liquid crystal display device was manufactured inthe same manner as that in Example 5 except that various polyamide acidmethyl esters synthesized in accordance with the raw materialcompositions shown in Table 6 below were used as the alignment controlfilm 109.

TABLE 6 Tetracarboxylic acid dianhydride Alignment Diamine compoundCompound control Compound group A groups B and C film No. (Mol %) (Mol%) R¹ n 6-1 A-1 (100) B-1 (70) —CH₃ — C-2 (30) — — 6-2 A-1 (100) B-2(80) —CH₃ — C-2 (20) — — 6-3 A-1 (100) B-5 (70) —CH₃ — C-5 (30) — — 6-4A-1 (50) B-15 (90) — — A-34 (50) C-6 (10) — — 6-5 A-29 (40) B-12 (90)—CH₂CH₃ — A-60 (60) C-4 (10) — —

Next, as a result of evaluating the display quality of the liquidcrystal display device according to this example, the aperture ratio washigher than that in the liquid crystal display device of Example 1, anda wide viewing angle at the time of the halftone display was confirmedas well as the high-grade display of 800:1 in the contrast ratio.Further, as a result of quantitatively evaluating the image-sticking andthe residual image relaxation time of the liquid crystal display devicesas in Example 1, the residual image relaxation time was 2 minutes orless in the use temperature range of 0° C. to 50° C., and stability ofalignment of the liquid crystal is higher than that of the otherexamples. Further, even in the visual image quality residual image test,the sticking of the image, and the display unevenness caused by theresidual image were not found at all, and the high displaycharacteristic equivalent to Example 1 was obtained.

While there have been described what are at present considered to becertain embodiments of the invention, it will be understood that variousmodifications may be made thereto, and it is intended that the appendedclaim cover all such modifications as fall within the true spirit andscope of the invention.

What is claimed is:
 1. A liquid crystal display device, comprising: apair of substrates, at least one of which is transparent; a liquidcrystal layer placed between the pair of substrates; an electrode group,formed on at least one of the pair of substrates, for applying anelectric field to the liquid crystal layer; and an alignment controlfilm placed on at least one of the pair of substrates, wherein thealignment control film is formed of polyimide and a precursor of thepolyimide, each of the polyimide and the precursor of the polyimidebeing obtained from a cyclobutanetetracarboxylic acid dianhydridederivative represented by the following chemical formula (1) andaromatic diamine as reactants, and the alignment control film isprovided with alignment capability by photo-alignment treatment:

where at least one of Z¹ to Z⁴ is a substituent represented by —NR₂,—SR, —OH, —COR, —(CH₂)_(n)—COOR, —CN, or —NO₂ (R's each independentlyrepresent a hydrogen atom or an alkyl group having a carbon number of 1to 4, and n represents an integer of 0 to 2), and the others arehydrogen atoms, wherein the aromatic diamine contains at least one kindof aromatic diamines selected from a compound group represented by thefollowing chemical formulae (102), (103), (104), (105), (106), (109) and(110):

where X's each independently have any one of the following structures:—CH₂—, —CO—, —O—, —NH—, —CO—NH—, —S—, —SO—, and —SO₂—.